Blue-black tetrazo dye and process of making same.



fonic acids enters into the reaction.

UNITED STATES PATENT OFF cE.

IVAN LEVINSTEIN ANDRICHARD HERZ, OF MANCHESTER, ENGLAND, ASSIGNORS TO THE LEvrNs'rEIN, LIMITED, 0E SAME PLACE.

BLUE-BLACK TETRAZQ DY E AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 634,009, dated October 3, 1899. 7

Original application filed June 14, 1897, Serial No. 640,753. Divided and this application filed January 3 1899. Serial No.

' 701,06 3. (Specimens-l To all whom it may concern.

Be it known that we, IVAN LEVINSTEIN, a citizen of the British Empire, and RICHARD 111332, a citizen of the German Empire, residing at Manchester, in the county of Lancaster, England, have invented certain new and useful Improvements in Coloringdllatters, (patented in Great Britain, N 0. 2,946, February 10, 1896; in France, No. 260,268, October 8, 1896, and in Germany May 28, 1896,) of which the following is a full, clear, and exact description.

This application is a division of our application filed June 14, 1897, Serial No. 640,753.

The production of an alpha alpha naphthylenediamin sulfonic acid is described in the specification of Letters Patent of Great Britain No. 15,444, dated the 14th day of August, A. D. 1893. This acid is obtained by the nitration of the acetyl compound. of alpha,- naphthylamin beta or beta, sulfonic acid and subsequent reduction and saponification. If treated with nitrous acid, it is decomposed and becomes incapable of reacting with amins or phenols. We have, however, discovered a new alpha alpha naphthylenediamin sulfonic acid which when treated with nitrous acid readily reacts with amins, diamins, their alkylated and phenylated compounds, with phenols, amidophenols, amidophenol ethers, and dioxy compounds both oi the benzene and naphthalene series, as well as their known carboxyl and sulfonic acids. In the new coloring-matters thus formed only one of the amide groups of the naphthylenediamin sul- The second amido group remains free. This second amido group may be further diazotized, and thus diazo-azo compounds may be produced which, combined with amins, diamins, their alkylated and phenylated compounds, with phenols, amidophenols, amidophenol ethers, dioxy compounds both of the benzene and naphthalene series, as well as their known carboxyl and sulfonic acids, produce tetrazo colors which dye shades from yellow to deep black and possess very valuable properties. These tetrazo colors may be employed either for developing the colors on the fiber or for the production of coloring-matters in substance.

The new alphaalpha naphthylenediamin sulfonic acid may be used not only for the production of a'zo and tetraz'o coloring-matters, but also, like all paradiamins, they may be employed in the manufacture of saifranins, indulins, and similar colors.

For the production of our new alpha alpha, naphthylenediamin monosulphonic acid we may proceed, by way of example, as follows: 9.3 kilos of anilin are dia'zotized in the usual well-known manner and the diazobenzene thus obtained is combined, while stirring, with 24.5 kilos of the sodium salt of alpha, naphthylamin beta monosulfonic acid dissolved in about five hundred liters of water. The temperature is preferably not allowed to exceed 15 centigrade. Stirring is continued for a few hours, when the formation of the coloring-matter is complete. The produced coloring-matter, which is in the form of a precipitate, is then filtered off and pressed.

- The thus-produced pressed cake is added to a boiling mixture of thirty kilos of iron borings, two hundred liters of water, and two kilos of ordinary commercial hydrochloric acid. hen the reaction is finished,the mass is made slightly alkaline by means of sodium carbonate or other suitable alkali, and the free anilin is recovered by steam in the wellunderstood manner. The remaining solution, which contains the sodium salt of the new naphthylenediamin sulfonic acid is then separated from the iron by filtration or otherwise. The filtrate is now acidified, when the new sulfonic acid crystallizes out in line needles having a slight red coloration.

In the manufacture of -coloringmatters i from our new sulfonic acid we may proceed as follows:

First step-23. 8 kilos of the new alpha. alpha naphth'ylenediamin sulfonic acid are dissolved in a solution of about 5.8 kilos of sodium carbonate in two hundred liters of water or of other suitable alkali in equivalent molecularproportion. Iceisadded,andwhen the mixture is cool the naphthylenediamin sulphonic acid is precipitated in a finelydivided state by means of one hundred kilos of acetic acid containing thirty per cent. acid. The mixture is well stirred and (liazotized by an aqueous solution of 7.2 kilos of sodium nitrite. The amidodiazonaphthalene' sulfonic acid separates out after some time as a difficultly-solublc powder of a brownish-yellow color. Instead of acetic acid, which we .preferto use, other suitable acid or acids may be employed.

Second step. The amidodiazonaphthalene sulfonic acid produced in the first step and obtained from 23.8 kilos of alpha, alpha naphthylenediamin sulfonic acid is added at ordinary temperature and while stirring to an alkaline solution of thirty-1i ve kilos of betanaphtholdisulfonicacidR. Thecombination begins at once and is completed within a short time. The coloring-matter thus obtained is salted out, filtered, pressed, and dried. It dyes wool in an acid-bath a blue color.

Other dyestuffs may be obtained in an analogous manner-if in place of betanaphthol disulfonic acid R other compounds are usedsuch, for example, as amins, diamins, their alkylated and phenylated compounds, amidophenols, amidophenol ethers, dioxy compounds both of the benzene and naphthalene series, as well as their known carboxyl and sulfonic acids. In such cases it will be obvious to chemists that equivalent molecular proportions to those hereinbefore specified should be employed.

Third step-Sixty-two kilos of the azo dyestuff prepared as above set forth and produced in the second step is dissolved in about three hundred liters of'water acidulated with seventy kilos of hydrochloric acid, 20 Baum. To the diluted solution, cooled with ice, there is gradually added a solution containing 7.2 kilos of sodium nitrite. The whole mixture is well stirred and kept ata low temperature. The solution, which was originally a violetblue, changes to a deep red. After a few hours the original dyestuff will be found to be completely transformed in the new diazoazo compound, which may either be at once used for combination or be precipitated by means of common salt. The diazo-azo compound, either in solution or in a precipitated form,is added while stirring to an alkaline solution of 14.5 kilos of betanaphthol. An excess of caustic alkali is to be avoided. After the reaction is completed the produced tetrazo coloring-matter is precipitated or may be completely separated as a dark-blue precipitate by means of common salt. It dyes wool in a neutral or acid bath a deep blue to black.

Analogous dyestuffs are produced if, in place of betanaphthol, other phenols or amins, diamins, or their alkylated or phenylated compounds, dioxy compounds both of the benzene and naphthalene series as well as their known carboxylic and sulfonio acids are used. If, for example, instead of 14. 5 kilos of betanaphtho], in step III, there is combined with the diazo compound 1%.5 kilos of bctanaphthylamin, and the combination is carried out in a sodium acetate solution, a coloring-lilatter is obtained which dies wool in a neutral or acid bath a deep black, which is distinguished by its fastness to milling and to light.

Having now particularly described and ascertained the nature of our said invention and in what manner the same is to be performed, we declare that what we claim is 1. The process for the production of a blueish-black tetrazo coloring-matter from the alpha, alpha naphthylenediamin beta,sulfonic acid which consists in diazotizing that acid, combining the resulting sulfonic acid with beta, naphthol beta betadisulfonic acid, rediazotizin g the thus-produced amidoazo coloring-matter, and finally combining theresulting diazo compound'with betanaphthol, substantially as described.

2. The process for the production of blue to deep black tetrazo coloring-matters from the alpha, alpha naphthylenediamin beta, sulfonic acid which consists in diazotizing that acid, combining the resulting sulfonic acid with beta, naphthol beta beta disulfonic acid, rediazotizing the thns-. produced amidoazo coloring-matter, and finally combining the resulting diazo compound with aromatic dyestuif components, substantially as described.

3. The process for the production of tetrazo coloring-matters from the alpha, alpha naphthylenediamin beta, sulfonic acid,which consists in diazotizing that acid, combining the resulting amidodiazonaphthalene sulfonic acid with color components of the naphthalene series,rediazotizing the thus-produced amidoazo coloring-matter, and combining the diazo product with hereinbefore-described aromatic dyestuff components, substantially as described.

at. The process for the production of a bluish-violet amidoazo coloring-matter from the alpha, alpha naphthylenediamin beta, sulfonic acid which consists in diazotizing that acid, and then combining the resulting amidodiazonaphthalene sulfonic acid with beta,

naphthol beta beta disulfonic acid, substanis a dark bluish-black powder with metallic luster soluble in water with a, blue color, and 1 in concentrated H 80 with a green color, is

1 In witness whereof We subscribe our signatures in presence of two Witnesses.

IVAN LEVIN STEIN. RICHARD HERZ.

Witn esses:

WILLIAM E. HEYs, ARTHUR MILLWARD. 

